Correlation of molecular organization and substrate wettability in the self-assembly of n-alkylsiloxane monolayers

Atul N. Parikh, Bo Liedberg, Sundar V. Atre, Moses Ho, David L. Allara

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93 Scopus citations

Abstract

Monolayers of n-octadecylsiloxane (CH3(CH2)17SiOxHy; ODS) were self-assembled from n-octadecyltrichlorosilane solutions onto a series of OH- and CH3-containing surfaces prepared from the self-assembly of controlled composition mixtures of HO(CH2)16SH and H3C(CH2)15SH on gold (RS/Au). Using null ellipsometry, infrared spectroscopy, and hexadecane contact angles; the coverages, chain structures, and surface wetting of the formed ODS assemblies were determined as a function of the OH fraction, fOH ≡ [OH]/[CH3 + OH], in the starting RS assembly. Three distinct ODS adsorption regimes were observed: (1) on pure CH3 surfaces no stable adsorbed layer forms; (2) for 0.1 ≲ fOH ≲ 0.8, the coverage is incomplete and monotonically increases with fOH and the ODS structures consist of a range of coexisting domains of nearly all-trans chains and disordered, liquid-like components with maximum disorder content, estimated as >80%, arising near fOH ∼ 0.5; and (3) for fOH > 0.8, a high coverage, close-packed monolayer is formed with predominantly all-trans chains tilted at 8-12° from the surface normal, a distinctly different tilt than the known value of 26-30° for the RS underlayer and an indication of strong structural decoupling (incommensurability) between the two highly organized layers. The fOH-dependence of the structures is explained on the basis of a previously proposed hypothesis that a continuous preadsorbed, substrate-bound water film is required for achieving maximum organization during n-alkylsiloxane self-assembly and that, in the present case of the OH/CH3 surfaces, the required water film structure at the preparation solution/substrate interface is not reached until high fOH values.

Original languageEnglish (US)
Pages (from-to)9996-10008
Number of pages13
JournalJournal of Physical Chemistry
Volume99
Issue number24
StatePublished - 1995
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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    Parikh, A. N., Liedberg, B., Atre, S. V., Ho, M., & Allara, D. L. (1995). Correlation of molecular organization and substrate wettability in the self-assembly of n-alkylsiloxane monolayers. Journal of Physical Chemistry, 99(24), 9996-10008.